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Journal of chromatography
Elesevier
Journal of chromatography

Elesevier

0021-9673

Journal of chromatography/Journal Journal of chromatographySCIISTPCCR
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    One-step synthesis of well-defined molecularly imprinted nanospheres for the class-selective recognition and separation of β-blockers in human serum

    Jin Y.Hou H.Sheng L.Huang Y....
    5页
    查看更多>>摘要:? 2022 Elsevier B.V.β-blockers are a class of medications that are used to treat abnormal heart rhythms and hypertension. Molecularly imprinted polymers (MIPs) capable of selective recognizing and extracting β-blockers from complex biological samples hold great promise in bioanalytical and biomedical applications, but developing such artificial receptor materials is still challenging. Herein, we introduce a simple one-step method for the synthesis of well-defined molecularly imprinted nanospheres in high yield (83.6–94.4%) via reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization for the selective recognition and extraction of the β-blockers from human serum. The prepared MIPs are characterized in terms of morphology, pore properties, binding kinetics, capacity, selectivity, and recognition mechanisms. The uniform nanoscale-imprinted layer favored the rapid mass transfer of β-blockers. The binding studies showed the high adsorption capacity (126.8 μmol/g) and selectivity of the developed nanomaterial. The investigation on the recognition mechanism reveals that multiple driving forces participate in the binding between MIP and β-blockers, where hydrogen bonding plays as the dominating role for the specific recognition. The MIP was successfully applied for the direct enrichment of five β-blockers from human serum with HPLC recoveries ranging from 82.9 to 100.3% and RSD of 0.5–6.9% (n = 3).

    Micellar electrokinetic chromatography method for the analysis of synthetic and phytocannabinoids

    Laanet P.-R.Vaher M.Saar-Reismaa P.
    5页
    查看更多>>摘要:? 2022 Elsevier B.V.Synthetic cannabinoids (SCs) are the largest group of illicit compounds currently monitored in Europe. Reliable analytical methods for the differentiation and quantification of SCs and phytocannabinoids (PCs) from plant-based products are needed to reduce possible public health risks. The objective of this research was to develop a new method for the detection of four SCs (JWH-018, JWH-073, JWH-200, JWH-250) and two PCs (THC, CBD) from plant materials by using micellar electrokinetic chromatography with UV-absorbance detection. A novel method with a water-based background electrolyte containing cholate micelles was developed and optimized using two sets of the Box-Behnken experimental design. The method enables the quantification of JWH-018, JWH-073, JWH-200, JWH-250, and detection of THC and CBD. The selectivity studies revealed that several plants that are prevalently used as carrier matrixes for SCs could be analyzed without an added sample purification procedure. A basic method validation was performed. The detection and quantification limits were 3.0 and 5.0 for SCs, and 3.7 and 6.2 mg/L for PCs. For all analytes, the method intra-day precision was under 8%, the inter-day precision under 13%, and recoveries up to 100%.

    Dispersive micro–solid–phase extraction of aflatoxins from commercial soy milk samples using a green vitamin–based metal–organic framework as an efficient sorbent followed by high performance liquid chromatography–tandem mass spectrometry determination

    Mohebbi A.Nemati M.Afshar Mogaddam M.R.Lotfipour F....
    5页
    查看更多>>摘要:? 2022 Elsevier B.V.In the current work, for the first time, a vitamin–based metal–organic framework constructed from cobalt ions and vitamin B3 has been used as a sorbent in dispersive micro–solid–phase extraction. The proposed method was used to extract and enrich aflatoxins (B1, B2, G1, and G2) from soy milk samples before their quantification by high performance liquid chromatography–tandem mass spectrometry. In this work, first the metal–organic framework was synthesized and characterized using techniques such as X–ray diffraction, Fourier transform infrared spectrophotometry, scanning electron microscopy, nitrogen adsorption/desorption, and energy–dispersive X–ray spectroscopy. Then it was used as an efficient sorbent in the proposed dispersive micro–solid–phase extraction. For this purpose, after precipitating the proteins of soy milk sample with the aid of trichloroacetic acid, the supernatant phase was taken, mixed with the synthesized sorbent, and vortexed. After centrifuging, the analytes loaded on the adsorbent were eluted with methanol to transfer them into an organic phase which was compatible with the subsequently employed separation system. The adsorption capacity of the synthesized MOF for aflatoxins B1, B2, G1, and G2 were 0.77, 0.83, 0.70, and 0.54 mg g–1, respectively. Under the best experimental situations, satisfactory outcomes including acceptable extraction recoveries (64–75%), low limits of detection (11.3–48.2 ng L–1) and quantification (42.8–161.6 ng L–1), and good repeatability (relative standard deviations equal or less than 4.0 and 4.7% for intra– and inter– day precisions, respectively) were obtained. In addition, green synthesis of the metal–organic framework (using vitamin B3 as a linker, water as the reaction solvent, and mild conditions) and usage low amount or volume of the adsorbent and organic solvents during the extraction process were the other beneficial aspects of this work which caused the suggested analytical method to be environmentally friendly.

    Hydroxyl-functionalized three-dimensional covalent organic framework for selective and rapid extraction of organophosphorus pesticides

    Yang C.Qian H.-L.Yan X.-P.Du M.-L....
    5页
    查看更多>>摘要:? 2022The wide utilization of organophosphorus pesticides (OPPs) results in a potential threat to ecosystem and human health. The essential extraction process in practical OPPs analysis always suffers from the low efficiency due to the limited accessible active sites and interactions in the adsorbents. Here, we report a rational design and synthesis of a novel hydroxyl-functionalized three-dimensional covalent organic framework (3D COF-OH) named JNU-6 with ordered porous structure and multiple interactions as the adsorbent for rapid and selective dispersive solid phase extraction (DSPE) of OPPs. The 3D COF-OH based DSPE was coupled with gas chromatography-flame thermionic detection (GC-FTD) for the determination of four selected OPPs with low limits of detection of 0.15–0.39 ng mL?1, wide linear range of 1–1100 ng mL?1. The developed method gave good precision (relative standard deviation of 1.6–8.5% (n = 5)) and recoveries of 86–106% for the determination of OPPs in complicated fruit and vegetable samples. This work reveals the high practical potential of functionalized 3D COFs as adsorbents for effective extraction of trace contaminants in complicated samples.

    Comparative study on retention behaviour and enantioresolution of basic and neutral structurally unrelated compounds with cellulose-based chiral stationary phases in reversed phase liquid chromatography-mass spectrometry conditions

    Perez-Baeza M.Escuder-Gilabert L.Martin-Biosca Y.Sagrado S....
    5页
    查看更多>>摘要:? 2022A comparative study on the retention behaviour and enantioresolution of 54 structurally unrelated neutral and basic compounds using five commercial cellulose-based chiral stationary phases (CSPs) and hydro-organic mobile phases compatible with MS detection is performed. Four phenylcarbamate-type cellulose CSPs (cellulose tris(3,5-dimethylphenylcarbamate), Cell1; cellulose tris(3-chloro-4-methylphenylcarbamate), Cell2; cellulose tris(4-chloro-3-methylphenylcarbamate), Cell4 and cellulose tris(3,5- dichlorophenylcarbamate), Cell5) and one benzoate-type cellulose CSP (cellulose tris(4-methylbenzoate), Cell3) are assayed. Mobile phases consist of binary mixtures of methanol (30–90% MeOH) or acetonitrile (10-98% ACN) with 5 mM ammonium bicarbonate (pH = 8.0). The existence of reversed phase (RPLC) and hydrophilic interaction liquid chromatography (HILIC) retention behaviour domains is explored. In MeOH/H2O mobile phases, for all compounds and CSPs, the typical RPLC retention behaviour is observed. When using ACN/H2O mobile phases, for all compounds in all CSPs (even in the non-chlorinated CSPs) a U-shaped retention behaviour depending on the ACN/H2O content is observed which indicates the coexistence of the RPLC- (< 80% ACN) and HILIC- (~80–98% ACN) domains. The magnitude of retention changes in both domains is related to the hydrophobicity of the compound as well as to the nature of the CSP. The study of the effect of the nature and concentration of the organic solvent, as well as the nature of the CSP on the enantioresolution reveals that: (i) the use of MeOH/H2O or ACN/H2O greatly affects the enantioselectivity and enantioresolution degree of the chromatographic systems, being, in general, better the results obtained with ACN/H2O mobile phases. (ii) The ACN-RPLC-domain provides much better enantioresolution than HILIC-domain. (iii) Cell2, especially with ACN/H2O mobile phases, is the CSP that allows baseline enantioresolution for a higher number of compounds. (iv) Phenylcarbamate-type CSPs do not offer clear complementary enantioselectivity to that of Cell2. (v) Cell3 is the only CSP that provides marked complementary enantioselectivity to that of Cell2, almost orthogonal in MeOH/H2O mobile phases.

    Enantioseparation of liquid crystals and their utilization as enantiodiscrimination materials

    Vankatova P.Kubickova A.Kalikova K.
    5页
    查看更多>>摘要:? 2022 Elsevier B.V.Liquid crystals can partake in enantioseparations in several different ways. Enantiomeric purity of chiral liquid crystals as analytes is often determined using enantioselective liquid or supercritical fluid chromatography. At the same time, chiral liquid crystalline materials can be applied as a chiral selector or they can function as an auxiliary material for a different chiral selector enabling enantioseparation of various solutes in miscellaneous separation techniques. They can also be used in fabrication of matrices or surfaces sensitive towards enantiomers or employed as chiral solvents for visualizing enantiomers in NMR. In this review, all of these aspects of relationship between liquid crystals and enantiodiscrimination are discussed in an effort to encompass their versatility and with emphasis on enantioseparations.

    Application of numerical simulation to solid phase-microextraction for decreasing of extraction time of pyrene and phthalate esters on solid coatings

    Jafari M.Jamshidian M.Habibi S.
    5页
    查看更多>>摘要:? 2022Reynolds-Averaged Navier-Stokes (RANS) approach with the k-ε closure model is employed for the first time to simulate direct Solid-Phase Micro-Extraction (SPME) computationally. Simulations are performed by using COMSOL Multiphysics in order to examine methods to decrease the extraction time. Experiments are also conducted to support data obtained from the numerical framework. Di-n-Butyl Phthalate (DNBP) and etched steel wire are chosen as the analyte and the adsorbent, respectively. Stirring rate, fiber's location, stirrer magnet's size, and the method of sample rotation are examined to decrease the extraction time. In addition, the effects of adding a baffle to the vial and implementing a periodic function for stirring the sample are studied. Increasing the stirring rate from 700 to 3000 rpm reduces the extraction time from 50 to 36 minutes. Present results suggest that changing the fiber's location and implementing a periodic stirring pattern significantly decrease the extraction time of SPME. The optimum fiber's location is found at 7.5 mm far from the vial's center, which leads to a 51% decrease in the extraction time. Furthermore, using a periodic stirring pattern results in a 60% decrease in the extraction time compared to the traditional uniform stirring pattern. To examine the robustness and reliability of the presented framework, two additional analytes, namely pyrene and Dioctyl phthalate (DOP), are chosen with one additional fiber, Al2O3. In this regard, the additional materials are used in the framework to investigate the effects of fiber's location and stirring pattern. By optimizing the fiber's location, the extraction time is reduced by 36% and 40% for SPME of pyrene and DOP, respectively. On the other hand, by using a periodic stirring pattern, the extraction time is reduced by 42% and 46% for SPME of pyrene and DOP, respectively.

    Peanut shells-derived biochars as adsorbents for the pipette-tip solid-phase extraction of endocrine-disrupting phenols in water, milk and beverage

    Sun R.Lu F.Yang Y.Qiao L....
    5页
    查看更多>>摘要:? 2022In the present work, a type of biochar materials derived from carbonizing peanut shells were obtained and employed as the adsorbents of pipette-tip solid-phase extraction (PT-SPE) for the enrichment and determination of six endocrine-disrupting phenols (EDPs) in combination with high-performance liquid chromatography equipped with ultraviolet detector (HPLC-UV). Abundant aliphatic and aromatic carbon structures and functional groups from polar heteroatoms (N, O, S) were distributed in the low-cost and eco-friendly peanut shells-derived biochar materials and were favorable for the enrichment of target EDPs. Moreover, the theoretical calculation based on density functional theory (DFT) proved that the effective enrichment of EDPs in aqueous samples benefited from the effective adsorption on the peanut shells-derived biochar materials. The experimental factors influencing the extraction efficiency were investigated, including adsorbent amount, aspirating/dispensing cycles, the type of elution solvent and elution times, salt addition, sample solution pH and type and volume of washing solvent. Under the optimal conditions, the proposed PT-SPE method exhibited good linear relationship (R2 > 0.993) in the range of 0.5–400 μg/L and low limits of detections (LODs) from 0.25 to 2.5 μg/L, as well as good precision and accuracy with relative standard deviations (RSDs) of 0.3%–13.2% and recoveries of 83.5%–117.1%. Finally, the biochars-based miniaturized pretreatment method was employed for the determination of six EDPs in bottled water, milk, tea beverage and disposal plastic bag soaked solution with recoveries from 77.5% to 116.5%.

    Extraction performance-structure relationship of polyamidoamine dendrimers on silica for online solid-phase extraction of organic pollutants

    Feng J.Sun H.Feng Y.Sun M....
    5页
    查看更多>>摘要:? 2022 Elsevier B.V.Polyamidoamine dendrimers with different generations (G1-G5) were synthesized in situ on silica progressively via Michael addition and amidation reactions. A sequence of materials was characterized by elemental analysis and Brunauer-Emmett-Teller test, the content of each element (C, H and N) was increased but the surface area was reduced gradually from G1 to G5. These materials were separately packed in a stainless steel column (10 × 4.0 mm, i.d.) for SPE. These SPE columns were combined with high performance liquid chromatography (HPLC) to establish an online SPE-HPLC analysis. According to the chemical structures of materials, polycyclic aromatic hydrocarbons (PAHs) and bisphenols as model analytes were selected to investigate the extraction performance and the extraction mechanism, so as to reveal the extraction performance-structure relationship of G1-G5. The extraction performance was improved with the increase of functional groups from G1 to G4 or G5, the hydrophobic effect played main role accompanied with possible weak hydrophilic, hydrogen-bonding and electrostatic interactions in extraction mechanism. The adsorption capacity, enrichment factor, partition coefficient and extraction efficiency for PAHs and bisphenols reached to 17.52 μg g?1 and 2.70 μg g?1, 5353 and 3002, 5066 and 1197, and 90.09% and 60.05% respectively. Compared with commercial SPE materials, these dendrimer-grafted silica materials were inferior to C18, but better than silica. Furthermore, the G4 and G5 were separately selected to develop two online SPE-HPLC analytical methods for determining trace PAHs and bisphenols in real water samples, and satisfactory results were obtained.

    Simultaneous quantification of plasma immunoglobulin subclasses for assessment of maternal and fetal immune response during pregnancy

    Huang J.Qi Y.Huang W.Zeng X....
    5页
    查看更多>>摘要:? 2022Measurement of immunoglobulin subclasses is a useful tool for exploring humoral immune deficiency in the presence of total immunoglobulins within reference intervals. Conventional methods for immunoglobulin measurement are mostly immunoassays, which are of low throughput and laborious to run multiple immunoglobulin subclass tests. Liquid chromatography-mass spectrometry (LC-MS) has emerged as a promising technology for the measurement of protein biomarkers in biological matrices, owing to its high specificity, selectivity, multiplexing, and wide dynamic range. In fully taking these advantages, we developed here a LC-MS based methodology for simultaneous quantitation of the primary immunoglobulin isotypes (IgG, IgA, IgM) and their subclasses in human plasma. Method validation demonstrated that the proposed method showed good linearity with R > 0.99, high precision with coefficients of variation for inter- and intra-assay less than 15%, as well as high accuracy with relative errors less than 8.7%. The developed method was further applied to maternal and cord blood collected at delivery for assessment of maternal and fetal immune status. The immunoglobulin profiles and the features of transplacental transport of maternal immunoglobulin subclasses were comparable to the findings from previous reports, further demonstrating the reliability of this method. Therefore, our method provides a competitive approach to high-throughput detection of multiple immunoglobulin subclasses for biomonitoring or epidemiological studies.